Bis-stilbene compounds

ABSTRACT

The present invention relates to new bis-stilbene compounds of the formula   WHEREIN R1 and R2 are identical or different and denote alkyl with 5 to 18 carbon atoms, substituted alkyl with a total of 2 to 20 carbon atoms, or alkenyl with 3 to 4 carbon atoms, X1 and X2 are identical or different and denote hydrogen, alkoxy with 1 to 4 carbon atoms, halogen, alkenyl with 3 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms, Y1 and Y2 are identical or different and denote hydrogen, halogen, alkenyl with 3 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms, a represents hydrogen, halogen, alkoxy with 1 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms, and the parapositions are free of alkoxy groups or R1O- and R2O- groups. The new compounds are useful as optical brighteners. This is a division of application Ser. No. 230,931, filed on Mar. 1, 1972, and now U.S. Pat. No. 3,843,718.

United States Patent n91 Luethi Dec. 16, 1975 1 BIS-STILBENE COMPOUNDS [75] Inventor: Christian Luethi, Muenchenstein,

I Switzerland Related US. Application Data [62] Division of Ser. No. 230,91, March 1, 1972, Pat.

[30] Foreign Application Priority Data Primary Examiner-Bernard l-lelfin Altamey, Agent, or Finn-Joseph G. Kolodny; Edward McC. Roberts; Prabodh l. Almaula [57] ABSTRACT The present invention relates to new bis-stilbene compounds of the fonnula Y x 1 (1) brecs-W R10 8. a

2 2 CH=C' wherein R, and R, are identical or different and denote alkyl with 5 to [8 carbon atoms, substituted alkyl with a total of 2 to 20 carbon atoms, or alkenyl with 3 to 4 carbon atoms, X, and X, are identical or different and denote hydrogen, alkoxy with l to 4 carbon atoms, halogen, alkenyl with 3 to 4 carbon atoms or alkyl with l to 4 carbon atoms, Y, and Y, are identical or different and denote hydrogen, halogen, alkenyl with 3 to 4 carbon atoms or alkyl with l to 4 carbon atoms, a represents hydrogen, halogen, alkoxy with l to 4 carbon atoms or alkyl with l to 4 carbon atoms, and the parapositions are free of alkoxy groups or R,O and R 0- groups. The new compounds are useful as optical brighteners.

l Claini, No Drawings alkyl or halogen. carboxyl, including its salts, carbalk- BIS-STILBENE COMPOUNDS oxy or carbophenoxy. carbonamido with an optionally substituted amido group, the sulpho group including its This is a division of application Ser. No. 230,931, salts, nitrile, halogen, hydroxyl or alkoxy and wherein filed on Mar. 1, 1972, and now US. Pat. No. furthermore X, represents hydrogen, alkoxy with 1 to 4 3,843,718. carbon atoms, halogen, alkenyl with 3 to 4 carbon The present invention relates to new bis-stilbene atoms or alkyl with 1 to 4 carbon atoms. Y, represents compounds, their use as optical brighten r and hydrogen or halogen, alkenyl with 3 to 4 carbon atoms cesses for their manufacture. or alkyl with l to 4 carbon atoms and wherein the French Pat. No. 1,576,018 already discloses bis-still0 para-positions are free of alkoxy groups or R 0 bene compounds of related structure and their usability groups. as optical brighteners. As a further development of b. Compounds of the formula Y Y X these investigations, some selected types of compound wherein R denotes alkenyl with 3 to 4 carbon atoms or have now been discovered which, because of special a substituted alkyl group with a total of 2-8 carbon substitution characteristics, display particularly advanatoms, whereof the substituents can be phenyl, phenyl tageous properties, above all for certain fields of use. substituted by lower alkyl or halogen, carboxyl includ- The new compounds according to the present invening its salts, carbalkoxy, carbonamido with an optiontion generally correspond to the formula ally substituted amido group, the sulpho group includramwmkca wherein R, and R are identical or different and denote ing its salts, nitrile, halogen, hydroxyl or alkoxy and alkyl with 5 to 18 carbon atoms, substituted alkyl with wherein furthermore X, represents hydrogen, alkoxy a total of 2 to 20 carbon atoms, or alkenyl with 3 to 4 with l to 4 carbon atoms or alkyl with l to 4 carbon carbon atoms, X, and X are identical or different and atoms and Y, represents hydrogen or halogen, and denote hydrogen, alkoxy with l to 4 carbon atoms, wherein the para-positions are free of alkoxy groups or halogen, alkenyl with 3 to 4 carbon atoms or alkyl with R,,O groups.

1 to 4 carbon atoms, Y, and Y are identical or difi'er- 40 c. Compounds of the formula bwmwwcrhcad R 0 0R4 ent and denote hydrogen, halogen, alkenyl with 3 to 4 wherein the substituents R,O occupy the positions 2 carbon atoms or alkyl with l to 4 carbon atoms, a or 3 and wherein R denotes carboxyl with 2 to 12 represents hydrogen, halogen, alkoxy with 1 to 4 carcarbon atoms or its alkali, ammonium and amine salts, bon atoms or alkyl with l to 4 carbon atoms, and the N-monoand N,N-di-(hydroxyalkyl)-carbonamidoalparapositions are free of alkoxy groups or R,() and kyl with 4 to 8 carbon atoms, sulphonic acid alkyl with R O groups. 2 to 4 carbon atoms or its alkali, ammonium and amine Preferred groups of compounds within the framesalts, X represents hydrogen, alkoxy with l to 4 carbon work of the formula l can be defined by the formulae atoms, chlorine, bromine, alkenyl with 3 to 4 carbon (2) to (5) listed below: atoms or alkyl with l to 4 carbon atoms, Y represents a. Compounds of the formula hydrogen, chlorine, bromine, alkenyl with 3 to 4 carwherein R denotes alkyl with 5 to 18 carbon atoms, bon atoms or alkyl with 1 to 4 carbon atoms and alkenyl with 3 to 4 carbon atoms or a substituted alkyl wherein the para-positions are free of alkoxy groups or group with a total of 2-12 carbon atoms, of which the R O groups.

substituents can be phenyl, phenyl substituted by lower (1. Compounds of the formula wherein the substituents R O- occupy the positions 2 or 3 and wherein R denotes carboxyalkyl with 2 to 12 carbon atoms or its alkali salts, carbalkoxyalkyl with up to 18 carbon atoms, sulphoalkyl with 2 to 3 carbon atoms (as the alkali salt or free acid), benzyl, which may be substituted by chlorine or by alkyl groups containing l to 4 carbon atoms, or alkenyl with 3 to 4 carbon atoms, X represents hydrogen or alkoxy with l to 4 carbon atoms and the para-positions are free of alkoxy groups or R -,O groups.

e. Compounds of the formula wherein R denotes alkyl with 5 to 12 carbon atoms, alkenyl with 3 to 4 carbon atoms, halogenoalkyl, cyanoalkyl or alkoxyalkyl with 2-6 carbon atoms, benzyl,

or benzyl substituted by chlorine or methyl, carboxyalkyl with 2 to 12 carbon atoms or its alkali, ammonium and amine salts, carbalkoxyalkyl with 2-l0 carbon atoms, carbophenoxyalkyl with l3 carbon atoms in the alkyl part and phenyl optionally substituted by methyl, carbonamidoalkyl with 2 to 4 carbon atoms, N-monoand N,N-di-(hydroxyalkyl)-carbonamidoalkyl with 4 to 8 carbon atoms, N-monoand N,N-di-(alkyl)-carbonamidoalkyl with 2-l0 carbon atoms, which can optionally be substituted by dialkyl( l to 3 carbon atoms)-amino groups, N-phenyl-carbonamidoalkyl with l-3 carbon atoms in the alkyl part and optionally with chlorine as a substituent in the phenyl radical, sulphonic acid alkyl with 2-4 carbon atoms or its alkali, ammonium or amine salts, and X, represents hydrogen, chlorine, bromine, methoxy, alkyl with l-4 carbon atoms or alkenyl with 3-4 carbon atoms, and the parapositions are free of methoxy groups or R O groups.

In these formulae (3) to (6) it should be noted generally that unless more detailed comments are made the preferred halogen is chlorine, alkyl is to be understood as both straight-chain and branched alkyl, preferably with a non-branched carbon atom in the oz-position to the ether bridge and, in the case of substituted alkyl groups, the number of carbon atoms of the alkyl part is normally I to 18, preferably l to 4. Amongst possible alke nyl groups as provided, for example, for R the allyl group is preferred and amongst lower alkyl groups those with l to 4 carbon atoms are always to be understood, unless otherwise stated. Possible salts of carboxyl groups and sulpho groups are above all the alkali, alkaline earth, ammonium and amine salts. By

3 5 mula 40 is reacted with about 1 mol equivalent of a compound of the formula and about 1 mol equivalent of a compound of the formula with one of the symbols Z and Z denoting a O=CH group and the other denoting one of the groupings of the formulae 0 (12) CH -l|R and (13) wherein R represents an alkyl radical which is optionally substituted further, preferably an alkyl radical with up to 6 carbon atoms, an aryl radical, preferably a phenyl radical, a cycloalkyl radical, preferably a cyclohexyl radical or an aralkyl radical, preferably a benzyl radical.

In the abovementioned formulae, the symbols X X Y and Y have the meaning given earlier. R, and R have the meaning given for R and R under the formulae (2) and (3), with the restriction that the meaning of modified carboxyl groups (carbalkoxy, carbophenoxy and optionally substituted carbonamide group) is to be excluded.

The modification of the carboxyl groups is effected after condensation of the compounds (8) or (9) with the diphenyl component, by converting compounds according to the formulae (2) or (3) or subsidiary formulae. having free carboxyl groups. or their alkali salts, into corresponding acid halides and manufacturing the corresponding esters or amides therefrom in accordance with methods which are in themselves known.

In accordance with the reaction principle explained above. it is possible for example. to react dialdehydes of the formula with monofunctional compounds of the formula Y x 1 I (15) v or monoaldehydes of the formula with bifunctional compounds of the formula wherein V denotes one of the phosphorus-containing substituents of the formulae (l0), (ll), ([2) or (13).

The phosphorus compounds of the formulae (l5), (l6) and (19) here required as starting substances are obtained in a manner which is in itself known by reacting halogenomethyl compounds, preferably chloromethyl or bromomethyl compounds of the formula H -Halogen (21) li halogen ilalogerrCH wii fiialogen 3,927,l 19 7 8 with phosphorus compounds of the formulae dioxane, as well as dimethylsulphoxide, formamide and N-methylpyrrolidone. Polar organic solvents such as dimethylformamide and dimethylsulphoxide are partic- (23) R-O P O R ularly suitable. Some of the reactions can also be carried out in aqueous solution.

The temperature at which the reaction is carried out can vary within wise limits. lt is determined (a) by the inertness of the solvent used towards the reactants,

(24) R0- P -Q -R especially towards the strongly basic alkali compounds, (B) by the reactivity of the condensation partners and E (y) by the activity of the combination of solvent and base as a condensation agent.

In practice, accordingly, temperatures between about and 100C are in general used, especially if (25) F or dimethylformamide or dimethylsulphoxide are employed as solvents. The preferred temperature range is R to 60C. However, under certain circumstances higher temperatures can also be employed if this is desired for reasons of time saving or if a less active but 5) 20 cheaper condensation agent is to be employed. In principle, reaction temperatures in the range of 10 to R 180C are thus also possible.

. Strongly basic alkali compounds which can be used are above all the hydroxides, amides and alcoholates ln these formulae, R has the indicated meaning, with (preferably those of primary alcohols containing 1 to 4 radicals R bonded to oxygen being preferably lower carbon atoms) of the alkali metals, amongst which alkyl groups whilst radicals R directly bonded to phosthose of lithium, sodium and potassium are, for ecophorus are preferably aryl radicals such as benzene nomic reasons, of predominant interest. In principle, radicals. The phosphorus compound of the formula and in special cases, it is however also possible to em- (12) can also be obtained by reaction of halogenoploy successfully alkali sulphides and alkali carbonates,

methyl compounds, preferably chloromethyl or bromoarylalkali compounds, such as, for example, phenylmethyl compounds of the formulae (20), (21 or (22), lithium, or strongly basic amines (including ammonium with chlorodiphenylphosphine and subsequent reaction bases, for example trialkylammonium hydroxides). with an alcohol of the formula R-OH (the meaning of When using the processes described above for the R being as defined above), for example with methanol manufacture of asymmetrical derivatives (which are of or with water. lesser importance), the competing reaction of the three To manufacture compounds according to the forreactants in the first place yields mixtures of asymmetmula (2) it is possible to use, in particular, those of the rically substituted bis-stilbene compounds according to above-mentioned process variants according to which the formula (2) and the two corresponding symmetriabout 1 mol equivalent of a compound of the formula cally substituted bis-stilbenes. The separation of these components, if desired, is effected by fractional recrys- (27) Z tallisation, column chromatography and/or utilisation l 1 of the different behaviour of certain groups (for example carboxylic acid groups and sulphonic acid groups) is reacted with about on mol equivalent each of a com towards certain reagents (for example aqueous alkaline pound of the formula l7) and 18), with Z, denoting solutions).

a grouping of the formulae (10), l l 12) and 13). The aldehydes which are circumscribed, for example, A variant of particular practical importance is to use, by the formulae (l7) and (18), are not all known, but as the diphenyl components according to the formula the manufacture of a large number is described in the (19), those which correspond to the formula literature [see, for example, Ann. 401, page 91 to l 19 28) ll l wherein R' denotes an alkyl group with l to 6 carbon (1913); J. Pr. Ch. 77, page 364 to 366 1908); Ber. 38, atoms. page 1676 (1905); DRP 209,608; Ann. 357, page 313 The manufacturing process is advantageously carried to 383 (1907); J. Med. Chem. 12, page 420 to 424 out in inert solvents. As examples thereof, there may be 1969)]. They are obtained almost without exception mentioned hydrocarbons such as toluene and xylene or by etherification of the corresponding hydroxybenalcohols such as methanol, ethanol, isopropan u zaldehydes. Hitherto unknown aldehydes are also ob nol, glycols, glycol-ethers such as Z-methoxyethanol, tainable by analogous processes. The section dealing hexanols, cyclohexanol and cyclooctanol, and also with examples deals especially with the manufacture of ethers such as diisopropyl ether, tetrahydrofurane and some aldehydes.

9 Within the framework of the present invention, prering opening, for example, polyamides of the polycapferred practical significance attaches to the reaction rolactam type, and also polymers which are obtainable according to the formulae (17) to l9) of aldehydes both via polyaddition and via polycondensation, such of the fonnulae 5 as polyethers or polyacetals',

C]. Q-wo Q-cao Qcao on R 0 c1 OR'w do gem CH OR 'w R 0 OR W W wherein R denotes a lower alkyl group and R,,. c. Polycondensation products or precondensates represents an allyl, benzyl, acetic acid, propionic acid, based on bifunctional or polyfunctional compounds butyric acid, propylenesulphonic acid or alkyl group possessing condensable groups, their homocondensawith 8 to 18 carbon atoms, with 4,4'-di-(alkoxyphostion and co-condensation products, and after-treatphonomethyl)-di-phenyl, or the compounds according merit products, such as, for example, polyesters, espeto the formula (3) obtained therefr m, with c b l cially saturated (for example ethylene glycol terephgroups being appropriat l esterified idi d if thalic acid polyester) or unsaturated (for example mad i leic acid dialcohol polycondensates as well as their The w compounds d fi d above h a more or cross-linking products with copolymerisable vinyl monless pronounced fluorescence in the dissolved or finely Omers), nonjbranched as as branched (also based divided state. They can be used for the optical bright- ,polyhydnc alcohols 251 for example, alkyd ening of the most diverse synthetic, semi-synthetic or resms) polyesters Polyamldes (for example hexameth' natural organic materials or substances which contain ylenedlzimme adpate) maleate resms melamme such organic materials 40 ms, their precondensates and analogues, polycarbonates and silicones' The following groups of organic materials to the d l extent that an optical brightening thereof 18 relevant, d Polya dmon products Such as W yurethanes be d l f h t l h (crosslinked and non-crosslinked) and epoxide resins. may men asexamp e50 sue ma ena Swlt II. Semi-synthetic organic materials, for example,

out the list which follows being intended to express any cellulose esters of varying degrees of esterificafion restriction thereto: (so-called 2 /2-acetate or triacetate) or cellulose ethers,

regenerated cellulose (viscose or cuprammonium cel- SYNTHETIC ORGANIC HIGH MOLECULAR lulose), or their afier-treatment products, and casein MATERIALS m III. Natural organic materials of animal or vegetable polymen'sallon Products based .orgamc origin, for example based on cellulose or proteins, such Pounds comammg at one polyn'fensable carbon as cotton, wool, linen, silk, natural lacquer resins, carbon double bond, that IS to say then homopolymers Starch and Casein or copolymers as well as their after-treatment products Th Organic materials to b i ll b i ht d n P as, for example, Cross-linking, g g Fg be in the most diverse states of processing (raw materi- Hon prodycts, p ym blends, Products obtamed y als, semi-finished goods or finished goods). On the modific tio 0 l'eactlve E P for example p y other hand, they can be in the form of structures of the based on afi-unsaturated carboxylic acids or derivamost di shapes, h i to Say, f example tives of such carboxylic acids, especially on acrylic dominantly three-dimensional bodies such as sheets, COmPOImdS (Such p a y sters, 0 profiles, injection mouldings, various machined artiacrylic acid, acrylonitrile, acrylamides and their derivacles, chips, granules or foams, and also as predomitives or their methacryl analogues) on olefine hydronantly two-dimensional bodies such as films, foils, laccarbons (such as, for example, ethylene, propylene, quers, coverings, impregnations and coatings, or as styrenes or dienes, and also so-called ABS polymers), predominantly one-dimensional bodies such as filaand polymers based on vinyl and vinylidene comments, fibres, flocks and wires. The said materials can, pounds (such as, for example, vinyl chloride, vinyl on the other hand, also be in an unshaped state, in the alcohol and vinylidene chloride); most diverse homogeneous or inhomogeneous forms of b. Polymerisation products which are obtainable by ivision. ch as. for x mpl in the form f p w r 1 1 solutions, emulsions, dispersions, latices, pastes or waxes.

Fibre materials can, for example, be in the form of endless filaments (stretched or unstrctched), staple fibres, flocks, hanks, textile filaments, yarns, threads, fibre fleeces, felts, waddings, flock structures or woven textile fabrics or textile laminates, knitted fabrics and paper, cardboards or paper pulps.

The compounds to be used according to the inven tion are of importance, inter alia, for the treatment of organic textile materials, especially woven textile fab rics. Where fibres, which can be in the form of staple fibres or endless filaments or in the form of hanks, woven fabrics, knitted fabrics, fleeces, flock substrates or laminates, are to be optically brightened according to the invention, this is advantageously effected in an aqueous medium, wherein the compounds in question are present in a finely divided form, (suspensions, socalled micro-dispersions or possibly solutions). If desired, dispersing agents, stabilisers, wetting agents and further auxiliaries can be added during the treatment.

Depending on the type of brightener compound used, it may prove advantageous to carry out the treatment in a neutral or alkaline or acid bath. The treatment is usually carried out at temperatures of about to l40C, for example at the boiling point of the bath or near it (about 90C). Solutions or emulsions in organic solvents can also be used for the finishing, according to the invention, of textile substrates, as is practised in the dyeing trade in so-called solvent dyeing (padthermofix application, or exhaustion dyeing processes in dyeing machines).

The new optical brighteners according to the present invention can further be added to, or incorporated in, the materials before or during their shaping. Thus they can for example be added to the compression moulding composition or injection moulding composition during the manufacture of films, foils (for example milling into hot polyvinyl chloride) or mouldings.

Where fully synthetic or semi-synthetic organic materials are being shaped by spinning processes or via spinning compositions, the optical brighteners can be applied in accordance with the following processes:

Addition to the starting substances (for example monomers) or intermediates (for example precondensates or prepolymers), that is to say before or during the polymerisation, polycondensation or polyaddition,

Powdering onto polymer chips or granules for spinning compositions,

Bath dyeing of polymer chips or granules for spinning compositions,

Metered addition to spinning melts or spinning solutions, and

Application to the two before stretching.

The new optical brighteners according to the present invention can, for example, also be employed in the following use forms:

a. Mixed with dyestuffs (shading) or pigments (coloured pigments or especially, for example, white pigments), or as an additive to dye baths, printing pastes, discharge pastes or reserve pastes, or for the after treatment of dyeings, prints or discharge prints.

b. Mixed with so-called carriers", wetting agents, plasticisers, swelling agents, antioxidants, light protection agents, heat stabilisers and chemical bleaching agents (chlorite bleaches or bleaching bath additives).

c. Mixed with cross-linking agents or finishes (for example starch or synthetic finishes). and in combina- 12 tion with the most diverse textile finishing processes, especially synthetic resin finishes (for example creaseproof finishes such as wash-and-wear, permanentpress" or no-iron"), as well as flameproof finishes, soft handle finishes, antisoiling finishes or anti-static finishes, or antimicrobial finishes.

d. Incorporation of the optical brighteners into polymeric carriers (polymerisation, polycondensation or polyaddition products), in a dissolved or dispersed form, for use, for example, in coating compositions, impregnating compositions or binders (solutions, dispersions and emulsions) for textiles, fleeces, paper and leather.

e. As additives to so-called master batches".

f. As additives to the most diverse industrial products in order to render these more marketable (for example improving the appearance of soaps, detergents and pigments.

g. In combination with other optically brightening substances.

h. in spinning bath preparations, that is to say as additives to spinning baths such as are used for improving the slip for the further processing of synthetic fibres, or from a special bath before the stretching of the fibre.

i. As scintillators for various purposes of a photographic nature, such as, for example, for electrophotographic reproduction or supersensitisation and for the optical brightening of photographic layers, optionally in combination with white pigments, such as for example TiO if the brightening process is combined with textile treatment methods or finishing methods, the combined treatment can in many cases advantageously be carried out with the aid of appropriate stable preparations, which contain the optically brightening compounds in such concentration that the desired brightening effect is achieved.

In certain cases, the brighteners are made fully effective by an after-treatment. This can, for example, represent a chemical treatment (for example acid treatment), a thermal treatment (for example heat) or a combined chemical/thermal treatment. Thus, for example, the appropriate procedure to follow in optically brightening a series of fibre substrates, for example of polyester fibres, with the brighteners according to the invention is to impregnate these fibres with the aqueous dispersions (optionally also solutions) of the brighteners at temperatures below C, for example at room temperature, and to subject them to a dry heat treatment at temperatures above C, it being generally advisable additionally to dry the fibre material before hand at a moderately elevated temperature, for example at not less than 60C and up to about C. The heat treatment in the dry state is then advantageously carried out at temperatures between l20 and 225C, for example by heating in a drying chamber, by ironing within the specified temperature range or by treatment with dry. superheated steam. The drying and dry heat treatment can also be carried out in immediate succession or be combined in a single process stage.

The amount of the new optical brighteners to be used according to the invention, relative to the material to be optically brightened, can vary within wide limits. A distinct and durable effect is already achievable with very small amounts, in certain cases, for example, amounts of 0.000l percent by weight. However, amounts of up to about 0.8 percent by weight and 13 optionally up to about 2 percent by weight can also be employed. For most practical purposes, amounts between 0.0005 and 0.5 percent by weight are of preferred interest.

The new optical brighte ners are also suitable for use as additives for wash baths or to industrial detergents and domestic detergents, and can be added in various ways. They are appropriately added to wash baths in the form of their solutions in water or in organic solvents, or in a finely divided form as aqueous dispersions. They are advantageously added to domestic detergents or industrial detergents in any stage of the process of manufacture of the detergent, for example the so-called slurry before spray-drying the detergent powder, or during the preparation of liquid detergent combinations. They can be added both in the form of a solution or dispersion in water or other solvents and without auxiliaries, as a dry brightener powder. The brighteners can for example be mixed, kneaded or ground with the detergent substances and mixed in this form into the finished washing powder. They can how ever also be sprayed as a solution or pre-dispersion onto the finished detergent.

Possible detergents are the known mixtures of washactive substances such as, for example, soap in the form of chips and powders, synthetic detergents, soluble salts of sulphonic acid half-esters of higher fatty alcohols, arylsulphonic acids with higher and/or multiple alkyl substituents, sulphocarboxylic acid esters of medium to higher alcohols, fatty acid acylaminoalkylor -aminoarylglycerinesulphonates, phosphoric acid esters of fatty alcohols and the like. So-called builders" which can be used are, for example, alkali polyphosphates and polymetaphosphates, alkali pyrophosphates, alkali salts of carboxymethylcellulose and other soil redeposition inhibitors and also alkali silicates, alkali carbonates, alkali borates, alkali perborates, nitrilotriacetic acid, ethylenediaminotetraacetic acid, and foam stabilisers such as alkanolamides of higher fatty acids. Furthermore, the detergents can contain, for example: Antistatic agents, agents which protect the skin and restore fats, such as lanoline, enzymes, anti-microbial agents, perfumes and dyestuffs.

The new optical brighteners have the particular advantage that they are active even in the presence of active chlorine donors, such as, for example, hypochlorite, and can be used without significant loss of the effects in wash baths containing non-ionic detergents, for example alkylphenol-polyglycoLethers.

The compounds according to the invention are added in amounts of 0.005 to 1% or more, relative to the weight of the liquid or pulverulent, finished detergent. Wash liquors which contain the indicated amounts of the optical brighteners claimed, impart a brilliant appearance in daylight when used for washing textiles of cellulose fibres, polyamide fibres, cellulose fibres with a high quality finish, polyester fibres, wool and the like.

The wash treatment is carried out, for example, as follows:

The textiles indicated are treated for l to 30 minutes at 20 to 100C in a wash bath which contains I to g/kg of a synthetic composite detergent and 0.05 to 1% of the brighteners claimed, relative to the weight of the detergent. The liquor ratio can be 1:3 to 1:50. After washing, the textiles are rinsed and dried in the usual manner. The wash bath can contain 0.2 g/l of active chlorine (for example as hypochlorite) or 0.1 to 2 g/l of sodium perborate, as a bleaching additive.

14 In the examples parts, unless otherwise stated, are always parts by weight, and percentages always percentages by weight. Unless otherwise stated, the melting points and boiling points are uncorrected.

MANUFACTURE OF SOME BENZALDEHYDE ETHERS (STARTING PRODUCTS) The instructions below serve as examples of the manufacture of new aldehydes used in the subsequent examples.

A. 43.6 g of commercial sodium hydride (about 55% strength) are suspended in 800 ml of (anhydrous) dimethylformamide. 152 g of o-vanillin, diluted with 200 ml of dimethylformamide, are added dropwise over the course of 30 minutes at 20 to 25C whilst cooling and the mixture is stirred for a further 3 hours at 20 to 25C. 168 g of bromoacetic acid methyl ester are then run in over the course of half an hour whilst cooling and the mixture is thereafter stirred for a further 18 hours at 20 to 25C. After it has been poured out onto ice/water and the precipitate has been filtered off and rinsed with water, the product is dried in vacuo at 30 to 40C. 188 g of the aldehyde of the formula OCH2COOCH3 of melting point 78 to 81C are obtained. A sample for analysis melts at 81 to 82C after recrystallisation from heptane.

The methyl ester can be saponified to the free acid by saponification for 6 hours at 20 to 25C with a methanolicaqueous potassium hydroxide solution: Melting point of the free acid 120 to 122C (from water).

Analogously, for example, the aldehyde of the formula CHO Q 2 .50 la OCrl CH 2 1 can be manufactured by employing propanesultone in the reaction instead of a bromine compound.

B. 29 g of sodium methylate are suspended in 400 ml of anhydrous dimethylformamide. A solution of 76 g of Z-hydroxy-3-methoxy-benzaldehyde is added dropwise at 20 to 25C over the course of half an hour, 90 g of benzylbromide are mixed in and the mixture is kept at 20 to 25C for 20 hours, 50C for 30 minutes and to C for 30 minutes. 2,500 ml of water are then added followed by 50 ml of glacial acetic acid, and the oil is extracted with chloroform. After distilling off the solvent, the residue is fractionated, whereupon 76.5 g of 2-benZyloxy-3-methoxybenzaldehyde pass over at boiling point, 214 to 215C.

C. 183 g of m-Hydroxybenzaldehyde and 182 g of allyl bromide in 500 ml of absolute alcohol are kept under reflux for 5 hours in the presence of 210 g of potassium carbonate. The filtrate is freed of the alcohol on a rotary evaporator and is fractionally distilled. 3-m-Allyloxybenzaldehyde passes over at boiling ALDEHYDES MANUFACTURED ANALOGOUSLY point 0 to 34C (176 g) TO OTHER INSTRUCTIONS IN THE LITERATURE Further aldehydes manufactured according to Example A:

Melting Point Boiling Point (C l t (T) p (mm) Z-n-Octoxybenzaldehyde 194-6 I 2 Z-Carbomethoxymethoxyhenzaldehyde 54-5 3-Carbomethox ymethox benzalde hyde 31- 3 13 3-6 0.15 Sodium salt of 2-sulphopropoxybenzaldehyde Decomposition S-n-Octnxybenzaldehyde 204-) l 7 3-Carboxymethoxybenzaldehyde 1 14-6 Sodium salt of 3-sulphopropoxybenzaldehyde Decomposition 2-Carboxymethoxybenznldehyde I 29-3 1 Z-n-Octadecyloxy-B-methoxyhenzaldehyde 63-4 Sodium salt of 2-sulphopropoxy-3-methoxybenza1dehyde 185-7 2-(Z-Elhyl-hexyloxy)benzaldehyde 174-6 1 l 3-n-Pentoxy-X-alkylbenzaldehyde (Note 1) 132-8 005 2-(4-Bromo-n-butoxyJbenzaldehyde 154-5 1 l 2-( 3-Cyano-n-propoxy lhenzaldehyde -1 -2( B-Curboxy-n-propoxy )benzaldehyde 89-91 2( 3-Carbethoxy-n-propoxy lbenzaldehyde 128-30 0. l4 2-n-Dodecyloxy-3-alkylbenzaldehyde 176-95 0.2 Sodium salt of 2-sulphopropoxy-3.S-dimethylbenzaldehyde Decomposition Z-Carboxymeth oxy-3methyl-5-te rt.butylbenza1dehyde 150-3 0.05 Z-Carbomethox ymethoxy-B-methy I-S-terLbutylbenzalde- 133-7 0.05 hvde 2-Dodecyloxy-3.S-dichlorobenzaldehyde 178-84 0.15 2-Carboxymethoxy-3 .5-dichlorobcnza1dchyde 167-9 Z-Carbomethoxymethoxy-lS-dichlorobenzaldehyde 1 17-8 Sodium salt of 2-sulphopropoxy-X-croty1-benzaldehyde Decomposition (Note 1) Further aldehydes manufactured according to Example B:

Melting Point Boiling Point Z-Benzyloxy-X-crotyl-benzaldehyde (Note I 133-49 0.03

Further aldehydes manufactured according to Example C and according to methods from Liebigs Annalen. Vol. 401. pages 91 to 1 19 (1913).

Melting Point Boiling Point 1 p(mm) Z-Allyloxybenzaldehyde 1 36-7 13 2-Hydroxy-3-a1lylbenzaldehyde Z-Allyloxy-3-methoxybenzaldehyde 152-5 12 3-Hydr0xy-X-a1lylbenzaldehyde (Note 1 1 169-73 14 Z-Crotyloxybenzaldehyde 85-6 0.04 2-Hydroxy-X-crotylbenzaldehyde (Note 1) 190-5 12 Z-Allyloxy-S-bro mobenzaldehyde 3 8-9 2-Methoxymethoxybenzaldehyde, which distils at l39-140C at 15 mm pressure, was manufactured analogously to Example 7 of DRP 209,608.

2-Hydroxy-3,S-dimethylbenzaldehyde, melting point 2123C, was manufactured according to Example 7, British Pat. No. 794,885. 2-Hydroxy-3-methyl-5-p-tert- NOTE 1 .butylbenzaldehyde, which was purified by steam distil- The allyl rearrangement led to two different allyl lation and is liquid at room temperature, was also 0bisomers (presumably in the 2- and 4-position) which tained analogously to this example. were employed as a mixture in the reaction to give the distyrylbiphenyl derivatives claimed. EXAMPLE 1 Similarly, the 2-croty1 ether gave a mixture of, pre- 13.9 g of sodium methylate are suspended in ml sumably 3- and 5-crotyl, isomers, which were also furof anhydrous dimethylformamide. A solution of 18 g of ther etherified, and used, without separation. B-( 2-formylphenoxy1-acetic acid and 20 g of 4,4-bis- 6 (3 OCH COONa 18 are thus obtained. Melting point: 197 to 199C.

EXAMPLE 4 The acid chloride of the formula (38) can be con- 5 verted into corresponding esters of amides by reaction with alcohols. phenols or primary/secondary amines or ammonia in accordance with known methods. If, for example, it is reacted for 4 hours under reflux with twice the calculated amount of diethanolamine in dioxane, the product of the formula OCH COONa OCH 0 OCH C N(C1i CH Oxi) N( CHZCH2QHI) 2 of melting point 300C are obtained.

EXAMPLE 2 The compound (36) from Example I can be con- (w) (gr-ch 00H :1 on

verted into the free acid as follows: 18.3 g are dissolved in a warm mixture of 300 ml of dimethylformamide and is obtained after recrystallisation from dioxane-water.

On passing ammonia into a solution of the acid chloride in chlorobenzene at l l0C and filtering off the precipitate formed, the unsubstituted amide The following method of manufacture is suitable for I00 m1 of water and the solution is run into 300 ml of 40 amides and esters of carboxyalkyl-ethers of the bisstil- 2 N hydrochloric acid whilst stirring. The product which has precipitated is filtered off, dried and recrystallised from dimethylformamide-toluene. 12.1 g of the compound of the formula Q-cmca-Q-Q-cmcn T OCH COOJ OCH COOH are obtained. Melting point: 263 to 267C (decompothe solution is cooled to room temperature, a two-fold sition EXAMPLE 3 7 g of the free acid of the formula (37) in ml of 5 which crystallises out from the filtrate is filtered off. 6.9 6

g of the compound of the formula to three-fold excess of a primary or secondary amine or an alcohol, phenol or aniline which is optionally substituted by non-reactive groups is added, the mixture is first stirred for 1 to 2 hours at room temperature and then, in the case of amines or alcohols with a boiling point below C, for a further 1 to 4 hours just below this boiling point, and subsequently for a further 1 to 2 hours at the reflux temperature of the solvent. in most cases, the desired ester or amide derivative can be filtered off in an analytically pure form after cooling to 0-5C.

H=CH I OCH 0 which after two recrystallisations from dimethylfonn- EXAMPLE amide melts at 240 to 242C, are thus obtained. Distyryl-bi hen I derivatives of the resent inven- 14.5 g of sod|um methylate (97% pure) are s tion,whereol the s tarting aldehydes do ribt possess any pended 60 ml of anhydrous dlmethylformamlqe- 5 salt-fonning groups, are obtainable analogously but g of moctoxybenzaldehydif and 40 g of P with half the amount of sodium methylate. (dlmelhoxyphosphonomethyll'dlphenyl are dlssolved If instead of sodium methylate, potassium methylate in l75 ml Of dimethylformamide at 70C and tlllS SOlU- is employed and the mixture is poured out into water Whilst Slill Warm, is added dTOPWiSE Over the instead of into hydrochloric acid, the compound of the course of about 15 minutes to the above sodium methl0 f m 42 i b i d i h f f i potassium ylate suspension at to 40C. The mixture is then i stirred for a further 2% hours at 40 to 45C. 175 ml of water are added, the mixture is neutralised with glacial EXAMPLE 7 acetic acid, heated to refluxing and cooled to 05C, 15.7 g of potassium tert.-butylate are suspended in and the product which has precipitated is filtered off. 15 100 ml of anhydrous dimethylformamide; 8.1 g of m- After drying and recrystallisation from nonane, 24 g of allyloxybenzaldehyde, 8.1 g of o-allyloxybenzaldehyde the compound of the formula and 22.7 g of 4,4'-bis-(diethoxy-phosphonomethyl)- H=0H-CH=0H (41) 0(CH ).cH 0(CH )c are obtained. Melting point: 182 to 183C. diphenyl are dissolved in 100 ml of dimethylformamide 25 at 75C and this solution, whilst still warm, is added EXAMPLE 6 dropwise over the course of about 20 minutes to the 27.8 g of sodium methylate (97% strength) are susabove potassium tert.-butylate suspension at 20 to pended in 80 ml of anhydrous dimethylsulphoxide. 36 g 40C. The mixture is then stirred for a further 4 hours of o-(carboxypropyloxy)-benzaldehyde and 40 g of at 40C and poured Out into 750 ml of water, and the 4,4-bis-(dimethoxyphosphonomethyl)-diphenyl are material which gradually solidifies is filtered off. For dissolved in 200 ml of dimethylsulphoxide at 70C and purification, the dried crude product is dissolved in this solution, whilst still warm, is added dropwise over excess chlorobenzene, the solution is treated with 1 g of the course of about 30 minutes t th b v di fullers earth, the filtrate is concentrated until a precipimethylate suspension at 20 to C. The mixture is tate pp r and is then Cooled to 0-5C, and the then stirred for a further 3 hours at C. The reaction 35 product is filtered off and rinsed with petroleum ether.

mixture is poured out into 1,000 ml of 0.5 N hydrochlo- A m Xture Of the three compounds OCH CH CH Z 2 I H C=CH-Cd 0 OCH CH=CH ric acid, the whole is briefly heated to the boil and is thus obtained. This mixture shows advantages, in the gradually cooled to room temperature, and the solid is shade of brightening and in the solubility in plastics filtered off. The filter cake is dispersed in 1,000 ml of such as polyethylene, over the individual symmetrical water whilst still moist, treated with 500 ml of acetone compounds (43) and (45 and heated for one hour under reflux. After cooling to 2022C, the product is filtered off and rinsed with EXAMPLE 8 water. 1 1.7 g of sodium methylate (97% strength) are sus- 53.4 g of the product of the formula pended in 50 ml of dimethylsulphoxide. 41.2 g of 2-(4- H=CH-CH=CH (.2) Q 9 Q-(C1-l -COOH HOOC (CH 3 -O 3,927,l 19 21 22 bromobutoxy)-benzaldehyde and 37.2 g of 4.4'-biswith decolourisation with fullers earth, 25.7 g of a (diethoxyphosphonomethyl)-diphenyl are dissolved in mixture of the compound of the formula (CH 131: Br (CH 150 ml of dimethylsulphoxide at 70C and this solution 0 of a compound which is assumed to correspond to the is added dropwise to the above suspension over the formula OCH CH CH=CH H C=CHCH CH O course of about 30 minutes at to 25C. The whole and of a compound of the presumed formula OCH CH CH=CH 'Br- (CH -0 is then stirred for a further 4 hours at to C. The 25 are obtained. Since all three compounds show similar reaction mixture is then poured into 750 ml of water properties, th mixtur Can be employed. Without Sepaand stirred in an ice bath until the precipitated product ration, for brightening organic materials.

has solidified, and this product is filtered off, washed with water and dried in a vacuum cabinet at C. 32.4 The examples listed in Table 1 below can be manug of a product melting at 12l to 134C are thus ob- 30 factured in accordance with one of the methods detained. After a single recrystallisation from heptane, scribed earlier (see note in last column).

Table l a a s n 5 a 4 R 3%? CH=CHMCH=CHTQT R a R 2 RI '1 2 Compound No. R, R1.

The following text presents, by way of examples, a series of possible uses of the class of compounds claimed, without thereby intending to impose a restriction; compounds with copolymerisable or co-condensable groups, such as allyl, carboxyl or carbalkoxy can, if the addition to the organic material to be brightened is carried out appropriately, become copolymerised or co-condensed and thereby more resistant to migration.

EXAMPLE 9 0.25% of ethylenediaminetetraacetic acid. After rinsing and drying, the fabric shows a strong brightening effect of good fastness to acid and to chlonne.

The washing powder of the abovementioned composition can also contain the brightener of the formula (36) incorporated directly.

A strong brightening effect is also achieved if the washing process is carried out for 30 minutes at 20C.

Similar results are obtained with the compounds of the formulae (37), (64), (65), (66) or (86).

EXAMPLE 10 Cut pieces of polyamide 6, bleached wool and Koratron"-finished cotton are together treated for 10 minutes at 30C, using a liquor ratio of 1:20 in a bath which contains 0.1% of the brightener of the formula (37), calculated relative to the fibre material, and 0.5 g/l of sodium fluosilicate.

After rinsing and drying, the three fibre materials show a strong brightening effect of good fastness to light.

EXAMPLE l l A cotton article provided with a non-iron finish by means of an aminoplast resin is washed for 15 minutes, using a liquor ratio of 1:20, in a liquor warmed to 50C which contains the following additives per liter: 0.004 to 0.016 g of a brightener of the fomiula (36), 4 g ofa washing powder of the following composition:

l5.00% of dodecylbenzenesulphonate 10.00% of sodium laurylsulphonate 40.00% of sodium tripolyphosphate 25.75% of anhydrous sodium sulphate 7.00% of sodium metasilicate 2.00% of carboxymethylcellulose and 0.25% of ethylenediaminetetraacetic acid.

After rinsing and drying, the fabric shows a higher degree of whiteness in daylight than does the untreated material.

Similar results are obtained when using one of the compounds of the formulae (37), (53), (54), (61), (64), (65). (66), (86) or (96).

EXAMPLE l2 Brightening of cotton fabric in a rinsing bath containing an agent for imparting a soft handle:

Stock solution: 0.05 g of the compounds of the formula (88) is dissolved in 5 ml of a mixture of alcohol and dimethylformamide 1:1) and added to 20 ml of a 4% strength aqueous solution of di-(octadecyl)- dimethyl-ammonium chloride.

Bleached cotton fabric is rinsed for minutes at 20 to 25C, using a liquor ratio of 1:20, in an aqueous liquor which contains 5% of the above stock solution, and is subsequently dried at 80C. The fabric is strongly brightened, without a greenish tinge.

The compounds of the formulae (36), (37), (41), (67), (68), (69), (80), (86), (87), (88), (89) or (93) give similar effects.

EXAMPLE 13 A polyamide fibre fabric (Perlon Helanca) is washed for 15 minutes, using a liquor ratio of 1:20 in a liquor warmed to 50C which contains the following additives per litre:

0.004 to 0.016 g of the brightener of the formula 0.25 g of active chlorine (bleach solution) 4 g of a washing powder of the following composition: 15.00% of dodecylbenzenesulphonate 10.00% of sodium laurylsulphonate 40.00% of sodium tripolyphosphate 25.75% of anhydrous sodium sulphate 7.00% of sodium metasilicate 2.00% of carboxymethylcellulose and 0.25% of ethylenediaminetetraacetic acid. The polyamide fibre fabric is only introduced into the wash bath, warmed to 50C, 15 minutes after preparation of the latter. After rinsing and drying, the fabric shows a good brightening effect of good fastness to light.

A good brightening effect is also obtained if the washing process is carried out in the same manner, but at 25C.

28 The washing powder of the abovementioned composition can also contain the brightener of the formulae indicated above incorporated directly.

Similar results are obtained when using the compounds of the following formulae: (36), (37), (52), (62). (64), (65). (67). (82), (86) or (97).

EXAMPLE l4 Polyacrylonitrile fibres (Orlon 42 or Courtelle) are introduced, using a liquor ratio of 1:40, into an aqueous bath which per litre contains 1 g of 85% strength formic acid and 0.2% of the compound of the formula (96), calculated relative to the fibre weight. The treatment bath is heated to the boil over the course of 30 minutes and is kept at this temperature for a further 30 to 60 minutes. After rinsing and drying, polyacrylonitrile fibres showing an excellent brightening effect are obtained.

Good brightening effects are also obtained if Courtelle fibres are treated in accordance with this example.

EXAMPLE 15 A polyamide fibre fabric (Perlon) is introduced, using a liquor ratio of 1:40, into a bath at 60C which contains 0.1% (relative to the weight of fabric) of the brightener of the formula (97) and also contains, per litre, l g of strength acetic acid and 0.25 g of an addition product of 30 to 35 mols of ethylene oxide to one mol of technical stearyl alcohol. The mixture is warmed to the boil over the course of 30 minutes and kept at the boil for 30 minutes. After rinsing and drying, a strong brightening effect of good fastness to light is obtained.

if instead of the polyamide-6 fabric a polyamide-6,6 (Nylon) fabric is used, similar good brightening effects are obtained.

Finally, the treatment can be carried out under HT- conditions, for example for 30 minutes at 130C. For this type of use, it is advisable to add 3 g/l of hydrosulphite to the liquor.

Similar results are obtained with the compounds of the formulae (36), (37), (43), (45), (52), (53), (54), (56), (57), (62) to (67), (73) (82), (86) and (92).

EXAMPLE l6 Polypropylene fibres or polyethylene fibres are treated, using a liquor ratio of 1:40, with 0.02 to 0.4% of the compound of the formula (68), (73) or (82) for 60 minutes, at 60 to l00c, in a bath which per litre contains 5 g of an addition product of about 35 mols of ethylene oxide to 1 mol of octadecyl alcohol and 0.5 g of trisodium phosphate. The material is then rinsed and dried. The polyolefine fibres thus obtained possess a substantially higher degree of whiteness than the untreated fibres.

lf instead of 0.5 g of trisodium phosphate 1 g of 85% strength formic acid is used, a similar effect is obtained.

EXAMPLE 17 A cellulose acetate fabric is introduced, using a liquor ratio of l :30 to 1:40, into an aqueous bath at 50C which contains 015% of the bis-stilbene compound of the formula 36), relative to the fibre material. The temperature of the treatment bath is brought to -95C and maintained thereat for 30 to 45 minutes. After rinsing and drying, a good brightening effect is obtained.

Similar effects are achieved with the compounds of the formula (37), (64), (65), (89), (90), (96) or (97).

EXAMPLE l8 Bleached wool fabric is treated, using a liquor ratio of 1:40, for 60 minutes in a bath which contains 0.1 to 0.4% of the brightener of the formulae (66), (86) or (96), calculated relative to the fibre weight, and 4 g/l of hydrosulphide. After rinsing and drying, strong brightening effects of good fastness to light are obtained.

Strong brightening effects are also obtained if instead of the hydrosulphite 5% of acetic acid, calculated relative to the fibre weight, are added to the bath.

EXAMPLE 19 A nylon-6 fabric is impregnated with the following liquor at room temperature on a padder, and squeezed out to a weight increase of 140%: 5 g/l of the brightener ofthe formula (41), (43), (45), (57), (62), (73). (91), (92), (94), (95) or (97), 5 g/l of lactic acid and 20 g/l of the reaction product of 1 mol of diethanolamine to coconut fatty acid, made up to one litre with perchloroethylene. The brightener is worked into a paste with the surface-active agent and the lactic acid and is then added to the organic solvent.

Following the padding and drying, the fabric is steamed for 3 minutes at 120C.

The substrate shows a good brightening effect.

Instead of the steaming process, the fabric can also be thermofixed for 30 seconds at 190C.

EXAMPLE 20 A fabric of polyvinyl chloride fibres (Thermovyl) is padded at room temperature (about 20C) with an aqueous dispersion which per litre contains 1 to 2 g of the compound of the formula (92) and l g of an addition product of about 35 mols of ethylene oxide to 1 mol of octadecyl alcohol, and is dried at about 70C. The dry material is subsequently subjected to a heat treatment for 3 minutes at 100C. The fabric of polyvinyl chloride fibres treated in this way has a substantially higher degree of whiteness than an untreated fabric of polyvinyl chloride fibres.

Similar results are achieved with the compounds of the formulae (43), (57), (61), (62), (67), (93), (94) or (97).

EXAMPLE 21 A polyester fabric (for example Dacron") is padded at room temperature (about 20C) with an aqueous dispersion which per litre contains 0.1 to l g of the compound of the formula (56) and l g of an addition product of about 35 mols of ethylene oxide to 1 mol of octadecyl alcohol, and is dried at about 100C. The dry material is subsequently subjected to a heat treatment at about 220C for 30 seconds. The polyester fabric treated in this way shows a strong optical brightening effect.

Similar results are obtained on using the compounds of the formulae (57), (58), (73), (82) or (95).

EXAMPLE 22 10,000 g of a polyamide in chip form, manufactured in a known manner from hexamethylenediamine adipate, are mixed with 30 g of titanium dioxide (rutile modification) and 5 g of the compound of the formula (68) for 12 hours in a tumbler vessel.

The chips treated in this way are fused in a kettle heated to 300310C by means of oil or diphenyl vapour, after displacing the atmospheric oxygen by steam, and the material is stirred for half an hour. The melt is thereafter extruded through a spinneret under a nitrogen pressure of 5 atmospheres gauge and the filament which has been spun in this way and cooled is wound up on a spinning bobbin. The filaments produced show an excellent brightening effect of good fastness to light.

if instead of a polyamide manufactured from hexamethylenediamine adipate a polyamide manufactured from e-caprolactam is used, similarly good results are obtained.

Similar results are achieved with the compound of the formula (36), (37), (40), (45), (49), (52) to (57), (61), (67), (72), (86) or (91) to (97).

EXAMPLE 23 100 g of fibre grade" polypropylene are intimately mixed with 0.8 g of the compound of the formula (68) and the mixture is fused at 280 to 290C whilst stirring. The melt is spun through customary spinnerets in accordance with melt spinning processes which are in themselves known, and the spun material is stretched.

Strongly brightened polypropylene fibres are obtained.

Similar results are achieved with the compounds of the formulae (49), (57), (61), (62), (63) or (92) to (95).

EXAMPLE 24 A 13% strength casting composition of acetylcellulose in acetone which contains relative to the dry weight of plastic 2% of anatase (titanium dioxide) as a delustring agent and 0.04% of the compound of the formula (72), is cast on a glass plate and spread by means of a metal rod to give a thin film. After drying, the film shows a substantially higher degree of whiteness than a film manufactured in the same way which does not contain an optical brightener.

Similar results are obtained on using the compounds ofthe formulae (43), (45), (56), (57), (62), (63), (91) to (94) or (97).

EXAMPLE 25 100 parts of polystyrene and 0.1 part of the compound of the formula (93) are fused in a tube of 1 cm diameter for 20 minutes at 210C, with exclusion of air. After cooling, an optically brightened polystyrene composition of good fastness to light are obtained.

Similar brightening effects are obtained when using a compound of the formulae (57), (62), (63), (67), (68), (91), (92) or (94).

EXAMPLE 26 100 parts of polyethylene are milled on a calender, warmed to C. to give a homogeneous hide. 0.02 part of the compound of the formula (61) are worked into this hide slowly. After the optical brightener has become uniformly distributed, the hide is pulled off the calender and then pressed in a heating press at 130 to C to give sheets.

Strong brightening effects are obtained. The compounds ofthe formulae (62), (63), (68) or (80) can be employed in the same way.

3 ,9 27, 1 l 9 31 32 X MP 27 verted into a viscous mass by means of a high speed stirrer.

mg of the compound of the formula (56) are added to 50 g of this 20% strength PAC solution. This mixture 1.5 g of a delustring agent, 1 g of titanium dioxide (rutile type) and 0.05 g of the compound of the formula.(43) are Stirred l a Pdymtha'? coating 5 is homogenised by stirring and is then left to stand for Posmon of 133 g of polyester l hour in order to allow the air bubbles produced to 26.7 g of ethyl acetate, 2 g of a reaction accelerator and diffuse 2 gofpolyfunctional isocyanate asacrosslinking agent. Thereafter the composition is cast on a glass plate This mixture is left to stand for 2 hours and is then and Spread by means ofa metal rod to give a uniform spread by means of a knife or a film-spreading rod onto film.

a cotton fabric (wet film thickness 1 mm). Thereafter The C fi| i h d i d i a d i bi f the Coat ng i dried o 24 ou at room temperature. approx. minutes at 50C with ventilation (air extrac- The fabric Coated in this way ShO a S g OPIiCaI tion) and then at room temperature with slight ventilabrightenlng effect tion. The PAC film can then be removed easily from Similar results are Obtained on using the compounds the glass plate. It has a substantially higher degree of Of the formulae I0 0f whiteness than the film manufactured in the same way (97). which does not contain the optical brightener.

Similar results are obtained when using the com- EXAMPLE pounds of the formulae (37), (43), (45), (53), (54),

An intimate mixture of 100 parts of polyvinyl chl0- (58), (62), (72), (86), (91) (92), (94), 96) or (97). ride, 3 parts of stabiliser (Advastat ED 100: Ba/Cd lclaim: complex), 2 parts of titanium dioxide, 59 parts of diocl. Bis-stilbene compounds of the formula tyl phthalate and 0.01 to 0.2 part of the compound of wherein R, and R are identical or different and denote the formula (43) are milled on a calender at 150 to alkyl with 5 to 18 carbon atoms, substituted alkyl with 155C to give a sheet. The opaque polyvinyl chloride a total of 2 to 20 carbon atoms of which the substitusheet thus obtained has a substantially higher degree of cuts are phenyl or phenyl substituted by lower alkyl or whiteness than a sheet which does not contain the optihalogen, or alkenyl with 3 to 4 carbon atoms, X, and X cal brightener. are identical or different and denote hydrogen, alkoxy The compounds of the form l (45 (49), (53), with l to 4 carbon atoms, halogen, alkenyl with 3 to 4 (56) t (58), (61) t (65 (67), (68 (72), (9]) to carbon atoms or alkyl with l to4carbon atoms, Y, and

97 give similar ff Y are identical or different and denote hydrogen, halogen, alkenyl with 3 to 4 carbon atoms or alkyl with l to EXAMPLE 29 4 carbon atoms, a represents hydrogen, halogen, alkoxy with l to 4 carbon atoms or alkyl with l to 4 carbon 7 g of anatase (TiO followed by 350 g of polyacrylatoms, and the parapositions are free of alkoxy groups onitrile polymer (=PAC) in powder form are added to or R,Oand R O- groups.

1,400 ml of dimethylformamide; the mixture is con- 

1. BIS-STILBENE COMPOUNDS OF THE FORMULA 